CN103664838B - A kind of ketene prepares the method for 2-acetofuran - Google Patents
A kind of ketene prepares the method for 2-acetofuran Download PDFInfo
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- CN103664838B CN103664838B CN201310685941.9A CN201310685941A CN103664838B CN 103664838 B CN103664838 B CN 103664838B CN 201310685941 A CN201310685941 A CN 201310685941A CN 103664838 B CN103664838 B CN 103664838B
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- ketene
- acetofuran
- furans
- organic solvent
- acylation catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Furan Compounds (AREA)
Abstract
A kind of ketene prepares the method for 2-acetofuran, under acylation catalyst exists, furans and ketene in organic solvent temperature control 5 ~ 20 DEG C react 2 ~ 5 hours, prepare 2-acetofuran crude product, then prepare 2-acetofuran product through Distillation recovery organic solvent and rectifying; Acylation catalyst be selected from phosphoric acid, sulfuric acid or tosic acid one or more, the mass ratio of acylation catalyst and furans is 0.005 ~ 0.009: 1; Furans and ketene mass ratio are (1.62 ~ 1.69): 1; Organic solvent be selected from methylene dichloride, ethylene dichloride or chloroform one or more.Relative to prior art, the present invention has the following advantages and beneficial effect: 1. raw materials cost is lower, is applicable to continuous prodution; 2. temperature of reaction is lower, is applicable to suitability for industrialized production; 3. production process does not produce hydrogenchloride or acetic acid, corrosion is less, and three waste discharge is few; 4. solvent is directly applied mechanically after returning, and achieve greenization synthesis, product yield reaches 95.0%, and purity reaches 99%.
Description
Technical field
The present invention relates to a kind of production method of chemical intermediate 2-acetofuran.
Background technology
2-acetofuran is important medicine, agricultural chemicals, fragrance intermediates, is the main raw material of synthesis SMIA.
The synthesis technique of 2-acetofuran mainly contains Acetic: Helvetica Chimica Acta, 88 (8), 2232-2287,2005, Tetrahedron, 60 (48), 10843-10850,2004, Synthesis, (13), 2165-2168, mentions in 2004 grades; Acetyl chloride method: Synthetic Communications, 38 (2), 255-264, mention in 2008; Acetic anhydride method: Chinese microbiotic magazine 30(5), 304-313, mentions in 2005, CN101357910A etc.
Acetic conversion rate of products and yield low, be up to 40% in furans, seriously corroded, production cost are high, quality product is low.
Acetyl Chloride 98Min. route adopts Acetyl Chloride 98Min. to be acylating agent, and reaction generates 2-acetofuran at a lower temperature, and yield can reach more than 90%.But Acetyl Chloride 98Min. is expensive, building-up process produces hydrogenchloride, seriously corroded, and pyridine or triethylamine need be adopted as solvent and de-acidying agent, and the three wastes are more, and solvent recuperation is complicated, and production cost is high.
Acetic anhydride method is owing to have passed through twice acylation process, and the transformation efficiency of furans has exceeded 95%, quality product also comparatively Acetyl Chloride 98Min. route be high.But this method raw material availability too low (utilization ratio of aceticanhydride is only 50%), the production efficiency of reactor is low, and production cost is too high.
Summary of the invention
For the above-mentioned defect of prior art, the invention provides yield and purity is high, pollute the method that little a kind of ketene prepares 2-acetofuran.
Reaction equation of the present invention is:
The object of the invention is to be realized by following scheme: under acylation catalyst exists, furans and ketene in organic solvent temperature control 5 ~ 20 DEG C react 2 ~ 5 hours, prepare 2-acetofuran crude product, then through Distillation recovery organic solvent and purification 2-acetofuran product; Described acylation catalyst be selected from phosphoric acid, sulfuric acid or tosic acid one or more; and the mass ratio of acylation catalyst and furans is 0.005 ~ 0.009: 1; described organic solvent be selected from methylene dichloride, ethylene dichloride or chloroform one or more.
Preferably, described furans and ketene mass ratio are (1.58 ~ 1.62): 1.
Preferably, described organic solvent be selected from methylene dichloride, ethylene dichloride or chloroform one or more, and organic solvent and furans mass ratio are (1 ~ 2.2): 1)
Preferably, described temperature of reaction is 10 ~ 20 DEG C.
Preferably, the described reaction times is 2 ~ 4 hours.
Preferably, described organic solvent is directly applied mechanically after reclaiming.
The acylation catalyst that the present invention uses, substantially increase reaction efficiency, not only the reaction times is starkly lower than literature value, and due to the interaction of acylation catalyst and ketene, temperature of reaction is obviously reduced.And experiment finds, the present invention uses ketene as reactant, can react in lower temperature (5 ~ 20 DEG C), and when conventional patents uses ketene as reactant, temperature of reaction is generally at 50 ~ 70 DEG C.In reaction process of the present invention, equipment running cost is low, little to the corrodibility of equipment.Relative to Acetic, Acetyl Chloride 98Min. route, acetic anhydride method, method of the present invention does not have the generation of by product, and product separation is relatively simple, and does not have the generation of spent acid waste liquid.To sum up, relative to prior art, the present invention has the following advantages and beneficial effect:
1. raw materials cost is lower, is applicable to continuous prodution;
2. temperature of reaction is lower, is applicable to suitability for industrialized production;
3. production process does not produce hydrogenchloride or acetic acid, corrosion is less, and three waste discharge is few;
4. solvent is directly applied mechanically after returning, and achieve greenization synthesis, product yield (in furans) reaches 95.0%, and purity reaches 99%.
Embodiment
In order to better explain the present invention, with the following Examples the present invention is further detailed, but the scope of protection of present invention is not limited to the scope represented in embodiment.
Embodiment 1
In the four-hole boiling flask that electric stirring, logical ketene gas pipe, thermometer and vapor pipe are housed, add 136g furans, 1.0 grams of phosphoric acid, 260g chloroforms, open and stir, within 3 hours, pass into ketene 85g at 15 DEG C.After normal pressure recycling design, decompression carry out rectifying, under-0.099Mpa, collect 78 ~ 81 DEG C of cuts, obtain purity be 99% 2-acetofuran 210.2g(yield count 95.5% with furans).
After solvent recuperation is directly applied mechanically 6 times, recycling design is applied mechanically and is seen the following form on the impact of product yield and purity:
| Apply mechanically number of times | Productive rate (%) | Purity (%) |
| 1 | 95.0 | 99.3 |
| 2 | 95.3 | 99.1 |
| 3 | 95.2 | 99.2 |
| 4 | 95.0 | 99.4 |
| 5 | 95.2 | 99.2 |
| 6 | 95.1 | 99.1 |
Embodiment 2
In the four-hole boiling flask that electric stirring, logical ketene gas pipe, thermometer and vapor pipe are housed, add 68g furans, 0.5 gram of phosphoric acid, 150g methylene dichloride, open and stir, within 3 hours, pass into ketene 42.0g at 20 DEG C.After normal pressure recycling design, decompression carry out rectifying, under-0.099Mpa, collect 78 ~ 81 DEG C of cuts, obtain purity be 99.1% 2-acetofuran 104.8g(yield count 95.2% with furans).。
Embodiment 3
In the four-hole boiling flask that electric stirring, logical ketene gas pipe, thermometer and vapor pipe are housed, add 136g furans, 1.0 grams of phosphoric acid, 280g methylene dichloride, open and stir, within 3 hours, pass into ketene 86g at 20 DEG C.After normal pressure recycling design, decompression carry out rectifying, under-0.099Mpa, collect 78 ~ 81 DEG C of cuts, obtain purity be 99.3% 2-acetofuran 209g(yield count 95.0% with furans).
Embodiment 4
In the four-hole boiling flask that electric stirring, logical ketene gas pipe, thermometer and vapor pipe are housed, add 136g furans, 1.2 grams of phosphoric acid, 260g chloroforms, open and stir, within 3 hours, pass into ketene 85.5g at 15 DEG C.After normal pressure recycling design, decompression carry out rectifying, under-0.099Mpa, collect 78 ~ 81 DEG C of cuts, obtain purity be 99.2% 2-acetofuran 211.2g(yield count 96.0% with furans).
Embodiment 5
In the four-hole boiling flask that electric stirring, logical ketene gas pipe, thermometer and vapor pipe are housed, add 136g furans, 0.8 gram of tosic acid, 270g chloroform, open and stir, within 4 hours, pass into ketene 84.5g at 10 DEG C.After normal pressure recycling design, decompression carry out rectifying, under-0.099Mpa, collect 78 ~ 81 DEG C of cuts, obtain purity be 99.5% 2-acetofuran 209.4g(yield count 95.2% with furans).
Embodiment 6
In the four-hole boiling flask that electric stirring, logical ketene gas pipe, thermometer and vapor pipe are housed, add 136g furans, 0.7 sulfuric acid, 136g ethylene dichloride, open and stir, within 5 hours, pass into ketene 86g at 10 DEG C.After normal pressure recycling design, decompression carry out rectifying, under-0.099Mpa, collect 78 ~ 81 DEG C of cuts, obtain purity be 99.3% 2-acetofuran 210.4g(yield count 95.6% with furans).
Below be only the part exemplary embodiments of this programme; those skilled in the art can adopt other embodiment to realize completely within the protection domain of the technical program; and all can make the appropriate adjustments parameters such as proportioning raw materials, temperature of reaction, times, just do not repeat one by one at this.
Claims (2)
1. a ketene prepares the method for 2-acetofuran, it is characterized in that, under acylation catalyst exists, furans and ketene in organic solvent temperature control 10 ~ 20 DEG C react 2 ~ 4 hours, prepare 2-acetofuran crude product, then through Distillation recovery organic solvent and purification 2-acetofuran product; Described acylation catalyst be selected from phosphoric acid, sulfuric acid or tosic acid one or more, and the mass ratio of acylation catalyst and furans is 0.005 ~ 0.009: 1; Described organic solvent be selected from methylene dichloride, ethylene dichloride or chloroform one or more; Described furans and ketene mass ratio are (1.62 ~ 1.69): 1; Described organic solvent and furans mass ratio are (1 ~ 2): 1.
2. ketene according to claim 1 prepares the method for 2-acetofuran, it is characterized in that, described organic solvent is directly applied mechanically after reclaiming.
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| CN104557808B (en) * | 2014-12-22 | 2017-01-04 | 广西中烟工业有限责任公司 | A kind of Preparation method and use of 2-acetyl furan |
| CN110551082A (en) * | 2019-08-15 | 2019-12-10 | 安徽金禾实业股份有限公司 | Preparation method of 2-acylfuran |
| CN116987044B (en) * | 2023-09-28 | 2024-01-26 | 山东亿嘉农化有限公司 | Synthesis process of 4- (p-chlorophenyl) -2-trifluoromethyl-3-oxazol-5-one |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1138681A1 (en) * | 2000-03-31 | 2001-10-04 | Council of Scientific and Industrial Research | A process for the preparation of acyl heteroaromatic compounds from heteroaromatic compounds by metal ion exchanged clays |
| CN101007762A (en) * | 2007-01-22 | 2007-08-01 | 山东汇海医药化工有限公司 | Method for synthesizing acetyl tributyl citrate from ketene |
| CN101357910A (en) * | 2008-09-19 | 2009-02-04 | 江苏爱利思达清泉化学有限公司 | Method for synthesizing 2-acetylfuran |
| CN101407468A (en) * | 2008-11-18 | 2009-04-15 | 扬子江药业集团有限公司 | Novel method for synthesizing aclatonium napadisilate |
| CN102295623A (en) * | 2011-05-26 | 2011-12-28 | 山东汇海医药化工有限公司 | Method for preparing N-acetylmorpholine by using ketene |
| CN102702143A (en) * | 2012-06-11 | 2012-10-03 | 四平市精细化学品有限公司 | Method for preparing 2-acetylfuran |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1138681A1 (en) * | 2000-03-31 | 2001-10-04 | Council of Scientific and Industrial Research | A process for the preparation of acyl heteroaromatic compounds from heteroaromatic compounds by metal ion exchanged clays |
| CN101007762A (en) * | 2007-01-22 | 2007-08-01 | 山东汇海医药化工有限公司 | Method for synthesizing acetyl tributyl citrate from ketene |
| CN101357910A (en) * | 2008-09-19 | 2009-02-04 | 江苏爱利思达清泉化学有限公司 | Method for synthesizing 2-acetylfuran |
| CN101407468A (en) * | 2008-11-18 | 2009-04-15 | 扬子江药业集团有限公司 | Novel method for synthesizing aclatonium napadisilate |
| CN102295623A (en) * | 2011-05-26 | 2011-12-28 | 山东汇海医药化工有限公司 | Method for preparing N-acetylmorpholine by using ketene |
| CN102702143A (en) * | 2012-06-11 | 2012-10-03 | 四平市精细化学品有限公司 | Method for preparing 2-acetylfuran |
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Denomination of invention: A method for preparing 2-Acetylfuran from vinyl ketone Effective date of registration: 20211130 Granted publication date: 20151021 Pledgee: Dongying Hekou District sub branch of China Post Savings Bank Co.,Ltd. Pledgor: SHANDONG HUIHAI PHARMACEUTICAL& CHEMICAL Co.,Ltd. Registration number: Y2021980013568 |